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Wildfire impacts on air quality and climate are expected to be exacerbated by climate change with the most pronounced impacts in the boreal biome. Despite the large geographic coverage, there is limited information on boreal forest wildfire emissions, particularly for organic compounds, which are critical inputs for air quality model predictions of downwind impacts. In this study, airborne measurements of 193 compounds from 15 instruments, including 173 non-methane organics compounds (NMOG), were used to provide the most detailed characterization, to date, of boreal forest wildfire emissions. Highly speciated measurements showed a large diversity of chemical classes highlighting the complexity of emissions. Using measurements of the total NMOG carbon (NMOG T), the Σ NMOG was found to be 50 % ± 3 % to 53 % ± 3 % of NMOG T , of which, the intermediate- and semi-volatile organic compounds (I/SVOCs) were estimated to account for 7 % to 10 %. These estimates of I/SVOC emission factors expand the volatility range of NMOG typically reported. Despite extensive speciation, a substantial portion of NMOG T remained unidentified (47 % ± 15 % to 50 % ± 15 %), with expected contributions from more highly-functionalized VOCs and I/SVOCs. The emission factors derived in this study improve wildfire chemical speciation profiles and are especially relevant for air quality modelling of boreal forest wildfires. These aircraft-derived emission estimates were further linked with those derived from satellite observations demonstrating their combined value in assessing variability in modelled emissions. These results contribute to the verification and improvement of models that are essential for reliable predictions of near-source and downwind pollution resulting from boreal forest wildfires. [ABSTRACT FROM AUTHOR]

Tailings ponds in the Alberta oil sands region are significant sources of fugitive emissions of methane to the atmosphere, but detailed knowledge on spatial and temporal variabilities is lacking due to limitations of the methods deployed under current regulatory compliance monitoring programs. To develop more robust and representative methods for quantifying fugitive emissions, three micrometeorological flux methods (eddy covariance, gradient, and inverse dispersion) were applied along with traditional flux chambers to determine fluxes over a 5-week period. Eddy covariance flux measurements provided the benchmark. A method is presented to directly calculate stability-corrected eddy diffusivities that can be applied to vertical gas profiles for gradient flux estimation. Gradient fluxes were shown to agree with eddy covariance within 18 %, while inverse dispersion model flux estimates were 30 % lower. Fluxes were shown to have only a minor diurnal cycle (15 % variability) and were weakly dependent on wind speed, air, and water surface temperatures. Flux chambers underestimated the fluxes by 64 % in this particular campaign. The results show that the larger footprint together with high temporal resolution of micrometeorological flux measurement methods may result in more robust estimates of the pond greenhouse gas emissions. [ABSTRACT FROM AUTHOR]

Tailings ponds in the Alberta Oil Sands Region are significant sources of fugitive emissions of methane to the atmosphere, but detailed knowledge on spatial and temporal variabilities is lacking due to limitations of the methods deployed under current regulatory compliance monitoring programs. To develop more robust and representative methods for quantifying these emissions, three micrometeorological flux methods were applied along with traditional flux chambers to determine fluxes over a 5-week period. Eddy covariance flux measurements provided the benchmark. A method is presented to directly calculate stability-corrected eddy diffusivities that can be applied to vertical gas profiles for gradient flux estimation. Gradient fluxes were shown to agree with eddy covariance within 7%, and inverse dispersion model fluxes within 11%, with an overall uncertainty of 28% for the calculated mean flux. Fluxes were shown to have only a minor diurnal cycle (18% variability) and to be mostly independent of wind speed, air and water surface temperatures. Flux chambers underestimated the fluxes by a factor of 2 in this particular campaign. These measurements indicate that the larger footprint of micrometeorological measurements results in more robust emission estimates representing the whole pond. [ABSTRACT FROM AUTHOR]

In this paper, measurements of air pollutants made at a ground site near Fort McKay in the Athabasca oil sands region as part of a multi-platform campaign in the summer of 2013 are presented. The observations included measurements of selected volatile organic compounds (VOCs) by a gas chromatograph–ion trap mass spectrometer (GC-ITMS). This instrument observed a large, analytically unresolved hydrocarbon peak (with a retention index between 1100 and 1700) associated with intermediate-volatility organic compounds (IVOCs). However, the activities or processes that contribute to the release of these IVOCs in the oil sands region remain unclear. Principal component analysis (PCA) with varimax rotation was applied to elucidate major source types impacting the sampling site in the summer of 2013. The analysis included 28 variables, including concentrations of total odd nitrogen (NOy), carbon dioxide (CO2), methane (CH4), ammonia (NH3), carbon monoxide (CO), sulfur dioxide (SO2), total reduced-sulfur compounds (TRSs), speciated monoterpenes (including α - and β -pinene and limonene), particle volume calculated from measured size distributions of particles less than 10 and 1 µ m in diameter (PM 10-1 and PM 1), particle-surface-bound polycyclic aromatic hydrocarbons (pPAHs), and aerosol mass spectrometer composition measurements, including refractory black carbon (rBC) and organic aerosol components. The PCA was complemented by bivariate polar plots showing the joint wind speed and direction dependence of air pollutant concentrations to illustrate the spatial distribution of sources in the area. Using the 95 % cumulative percentage of variance criterion, 10 components were identified and categorized by source type. These included emissions by wet tailing ponds, vegetation, open pit mining operations, upgrader facilities, and surface dust. Three components correlated with IVOCs, with the largest associated with surface mining and likely caused by the unearthing and processing of raw bitumen. [ABSTRACT FROM AUTHOR]

A mobile laboratory equipped with state-of-the-art gaseous and particulate instrumentation was deployed across the Greater Toronto Area (GTA) during two seasons. A high-resolution time-of-flight chemical ionization mass spectrometer (HR-TOF-CIMS) measured isocyanic acid (HNCO) and hydrogen cyanide (HCN), and a high-sensitivity laser-induced incandescence (HS-LII) instrument measured black carbon (BC). Results indicate that on-road vehicles are a clear source of HNCO and HCN and that their impact is more pronounced in the winter, when influences from biomass burning (BB) and secondary photochemistry are weakest. Plume-based and time-based algorithms were developed to calculate fleet-average vehicle emission factors (EFs); the algorithms were found to yield comparable results, depending on the pollutant identity. With respect to literature EFs for benzene, toluene, C2 benzene (sum of m- , p- , and o -xylenes and ethylbenzene), nitrogen oxides, particle number concentration (PN), and black carbon, the calculated EFs were characteristic of a relatively clean vehicle fleet dominated by light-duty vehicles (LDV). Our fleet-average EF for BC (median: 25 mg kg fuel-1 ; interquartile range, IQR: 10–76 mg kg fuel-1) suggests that overall vehicular emissions of BC have decreased over time. However, the distribution of EFs indicates that a small proportion of high-emitters continue to contribute disproportionately to total BC emissions. We report the first fleet-average EF for HNCO (median: 2.3 mg kg fuel-1 , IQR: 1.4–4.2 mg kg fuel-1) and HCN (median: 0.52 mg kg fuel-1 , IQR: 0.32–0.88 mg kg fuel-1). The distribution of the estimated EFs provides insight into the real-world variability of HNCO and HCN emissions and constrains the wide range of literature EFs obtained from prior dynamometer studies. The impact of vehicle emissions on urban HNCO levels can be expected to be further enhanced if secondary HNCO formation from vehicle exhaust is considered. [ABSTRACT FROM AUTHOR]

Aircraft-based measurements of methane (CH4) and other air pollutants in the Athabasca Oil Sands Region (AOSR) were made during a summer intensive field campaign between 13 August and 7 September 2013 in support of the Joint Canada--Alberta Implementation Plan for Oil Sands Monitoring. Chemical signatures were used to identify CH4 sources from tailings ponds (BTEX VOCs), open pit surface mines (NOy and rBC) and elevated plumes from bitumen upgrading facilities (SO2 and NOy ). Emission rates of CH4 were determined for the five primary surface mining facilities in the region using two mass-balance methods. Emission rates from source categories within each facility were estimated when plumes from the sources were spatially separable. Tailings ponds accounted for 45% of total CH4 emissions measured from the major surface mining facilities in the region, while emissions from operations in the open pit mines accounted for ~50 %. The average open pit surface mining emission rates ranged from 1.2 to 2.8 t of CH4 h-1 for different facilities in the AOSR. Amongst the 19 tailings ponds, Mildred Lake Settling Basin, the oldest pond in the region, was found to be responsible for the majority of tailings ponds emissions of CH4 (>70 %). The sum of measured emission rates of CH4 from the five major facilities, 19.2±1.1 tCH4 h-1, was similar to a single mass-balance determination of CH4 from all major sources in the AOSR determined from a single flight downwind of the facilities, 23.7±3.7 tCH4 h-1. The measured hourly CH4 emission rate from all facilities in the AOSR is 48±8% higher than that extracted for 2013 from the Canadian Greenhouse Gas Reporting Program, a legislated facility-reported emissions inventory, converted to hourly units. The measured emissions correspond to an emissions rate of 0.17±0.01 TgCH4 yr-1 if the emissions are assumed as temporally constant, which is an uncertain assumption. The emission rates reported here are relevant for the summer season. In the future, effort should be devoted to measurements in different seasons to further our understanding of the seasonal parameters impacting fugitive emissions of CH4 and to allow for better estimates of annual emissions and year-to-year variability. [ABSTRACT FROM AUTHOR]

In this paper, measurements of air pollutants made at a ground site near Fort McKay in the Athabasca oil sands region as part of a multi-platform campaign in the summer of 2013 are presented. The observations included measurements of selected volatile organic compounds (VOCs) by a gas chromatograph &ndash ion trap mass spectrometer (GC-ITMS). This instrument observed a large, analytically unresolved hydrocarbon peak (with retention index between 1100 and 1700) associated with intermediate volatility organic compounds (IVOCs). However, the activities or processes that contribute to the release of these IVOCs in the oil sands region remain unclear. Principal component analysis (PCA) with Varimax rotation was applied to elucidate major source types impacting the sampling site in the summer of 2013. The analysis included 28 variables, including concentrations of total odd nitrogen (NOy), carbon dioxide (CO2), methane (CH4), ammonia (NH3), carbon monoxide (CO), sulfur dioxide (SO2), total reduced sulfur compounds (TRS), speciated monoterpenes (including α- and β-pinene and limonene), particle volume calculated from measured size distributions of particles less than 10 µm and 1 µm in diameter (PM10-1 and PM1), particle-surface bound polycyclic aromatic hydrocarbons (pPAH), and aerosol mass spectrometer composition measurements, including refractory black carbon (rBC) and organic aerosol components. The PCA was complemented by bivariate polar plots showing the joint wind speed and direction dependence of air pollutant concentrations to illustrate the spatial distribution of sources in the area. Using the 95 % cumulative percentage of variance criterion, ten components were identified and categorized by source type. These included emissions by wet tailings ponds, vegetation, open pit mining operations, upgrader facilities, and surface dust. Three components correlated with IVOCs, with the largest associated with surface mining and is likely caused by the unearthing and processing of raw bitumen. [ABSTRACT FROM AUTHOR]

Aircraft-based measurements of methane (CH4) and other air pollutants in the Athabasca Oil Sands Region (AOSR) were made during a summer intensive field campaign between August 13 and September 7 2013, in support of the Joint Canada-Alberta Implementation Plan for Oil Sands Monitoring. Chemical signatures were used to identify CH4 sources from tailings ponds (BTEX VOC's), open-pit surface mines (NOy and rBC) and elevated plumes from bitumen upgrading facilities (SO2 and NOy). Emission rates of CH4 were determined for the five primary surface mining facilities in the region using two mass balance methods. Emission rates from source categories within each facility were estimated when plumes from the sources were spatially separable. Tailings ponds accounted for 45 % of total CH4 emissions measured from the major surface mining facilities in the region while emissions from operations in the open pit mines accounted for ~ 50 %. The average open pit surface mining emission rates ranged from 1.2 to 2.8 tonnes of CH4 hr-1 for different facilities in the AOSR. Amongst the 19 tailings ponds, Mildred Lake Settling Basin, the oldest pond in the region, was found to be responsible for the majority of tailings ponds emissions of CH4 (> 70 %). The sum of measured emission rates of CH4 from the five major facilities, 19.2 ± 1.1 tonnes CH4 hr-1, was similar to a single mass balance determination of CH4 from all major sources in the AOSR determined from a single flight downwind of the facilities, 23.7 ± 3.7 tonnes CH4 hr-1. The measured hourly CH4 emission rate from all facilities in the AOSR is 48 ± 8 % higher than that extracted for 2013 from the Canadian Green House Gas Reporting Program, a legislated facility-reported Emissions Inventory, converted to hourly units. The measured emissions correspond to an emissions rate of 0.17 ± 0.01 Tg CH4 yr-1, if the emissions are assumed temporally constant, an uncertain assumption. The emission rates reported here are relevant for the summer season. In future, effort should be devoted to measurements in different seasons to further our understanding of seasonal parameters impacting fugitive emissions of CH4 and to allow better estimates of annual emissions and year to year variability. [ABSTRACT FROM AUTHOR]

Organic acids are known to be emitted from combustion processes and are key photochemical products of biogenic and anthropogenic precursors. Despite their multiple environmental impacts, such as on acid deposition and human–ecosystem health, little is known regarding their emission magnitudes or detailed chemical formation mechanisms. In the current work, airborne measurements of 18 gas-phase low-molecular-weight organic acids were made in the summer of 2013 over the oil sands region of Alberta, Canada, an area of intense unconventional oil extraction. The data from these measurements were used in conjunction with emission retrieval algorithms to derive the total and speciated primary organic acid emission rates, as well as secondary formation rates downwind of oil sands operations. The results of the analysis indicate that approximately 12 t day−1 of low-molecular-weight organic acids, dominated by C1–C5 acids, were emitted directly from off-road diesel vehicles within open pit mines. Although there are no specific reporting requirements for primary organic acids, the measured emissions were similar in magnitude to primary oxygenated hydrocarbon emissions, for which there are reporting thresholds, measured previously ( ≈  20 t day−1). Conversely, photochemical production of gaseous organic acids significantly exceeded the primary sources, with formation rates of up to  ≈  184 t day−1 downwind of the oil sands facilities. The formation and evolution of organic acids from a Lagrangian flight were modelled with a box model, incorporating a detailed hydrocarbon reaction mechanism extracted from the Master Chemical Mechanism (v3.3). Despite evidence of significant secondary organic acid formation, the explicit chemical box model largely underestimated their formation in the oil sands plumes, accounting for 39, 46, 26, and 23 % of the measured formic, acetic, acrylic, and propionic acids respectively and with little contributions from biogenic VOC precursors. The model results, together with an examination of the carbon mass balance between the organic acids formed and the primary VOCs emitted from oil sands operations, suggest the existence of significant missing secondary sources and precursor emissions related to oil sands and/or an incomplete mechanistic and quantitative understanding of how they are processed in the atmosphere. [ABSTRACT FROM AUTHOR]